Treatment of clays



United States Patent TREATNIENT OF CLAYS William E. Brown, Gihsonia, and Clifford R. Giacobine,

Oakmont, Pa., assignors to Gulf Research & Development Company, Pittsburgh, Pa., a corporation of Delaware No Drawing. Application November 18, 1954, Serial No. 469,855

19 Claims. c1. zsz-i-ass This invention relates to a process of treating bodies comprised wholly or in part of clays, including clay-like materials, for the purpose of maintaining and/ or restoring the permeability to fluids of such bodies and rendering them stable toward disruption by mechanical and/ or chemical forces. More particularly,this invention relates to a process of treating bodies comprised wholly or in part of clays, including clay-like materials, subject to swelling and/or dispersion, with subsequent loss of permeability and reduction in mechanical strength, for the purpose of maintaining and/ or restoring the permeability to fluids of such bodies and rendering them stable toward disruption by mechanical and/ or chemical forces.

Clay-containing bodies often are substantially impermeable or have a low permeability to fluids or lose some or all of the permeability they may possess when they are subjected to the action of liquids such as water, certain brines, emulsions containing water or certain brines, etc. Treatment of such clay bodies in accordance with the process of this invention will render them permeable, prevent a reduction in fluid permeability and/or restore fluid permeability to those clay bodies in which it has been lost. As a result of the treatment the resistance of the clay bodies to mechanical and/or chemical disintegration will also be substantially increased.

The clay or clay-like materials which can be treated in accordance with our invention can include any natural geologic formations or artificial formations such as railroad or highway embankments, road beds and road surfaces, automobile parking areas, areas for outdoor sports, storage areas, military installations, etc. Included also among the materials which can be treated to improve or maintain their permeability and their physical and/ or chemical stability are manufactured articles containing clays or clay-like materials. As an example, but without being limited thereto, this process can be employed to treat articles cast, extruded or otherwise formed from clay to increase their mechanical strength prior to and/ or after firing.

The process of this invention has particular applicability in the treatment of natural geologic formations for the purpose of preventing or correcting the loss in permeability thereof caused by swelling and/or dispersing of the clay contained therein, preserving the approximate geometry of the grains of the formation, maintaining the pore distribution of the formation and firming the formation if it is uncemented or poorly cemented. More specifically, this invention is especially advantageous in the treatment of a clay-containing formation adjacent a borehole in wells in order to increase, maintain and/ or restore the permeability of the formation by rendering the Patented Sept. 4, 1956 clay contained therein resistant to swelling, disruption and/or migration, and also to shrink essentially irreversibly the hydrated, swollen clay which may be present in said formations adjacent wells producing fluids, such as hydrocarbons, water, etc., or in wells which are used to inject such fluids into a geologic formation. The clay in the formation can be that which was present originally, or it can be clay which was introduced. into the formation in the process of creating the borehole, e. g., by the use of a clay-containing drilling mud, or in subsequent operations.

The clay originally present in the formation can reduce the permeability of the formation by swelling and/ or migrating to form bridges or blocks in the pores of the formation or in perforations in casing, screens, etc., used in well completions, as a result of contact of said clay with aqueous liquids such as water, certain brines, emulsions containing water or certain brines, etc. This liquid can be introduced into the formation as drilling mud filtrate, injection water, water from leaks in or behind the casing, or ground water associated with the formation. Of particular concern in the case of introduced clay is that clay which, as a component of the drilling mud, invades the formation during the drilling of the borehole. High swelling montniorillonite is often used in drilling muds, among other reasons, because of its ability to create a low permeability filter cake on the formation. Under some conditions, a low permeability zone is created within the formation in the vicinity of the borehole from invasion by the drilling mud. In addition, if the mud filter cake is not removed completely when drilling has been completed, it forms a barrier to the flow of fluid into or out from the formation. The invention disclosed and claimed herein will shrink the hydrated, swollen clay in the formation, mud cake, and/or invaded zone so as to substantially increase the permeability and mechanical and chemical stability of the formation.

Among the clays which may be present originally in natural geological formations or may have been introduced therein and which can be effectively treated in accordance with the present invention there are included clay minerals of the montmorillonite group such as 'montmorillonite, saponite, nontronite, hectorite, and sauconite; the kaolin group such as kaolinite, nacrite, dickite, and halloysite; the hydrous-mica group such as hydrobiotite, glauconite, illite and bramallite; the chlorite group such as chlorite and chamosite; clay minerals not belonging to the above groups such as vermiculite, attapulgite, and sepiolite; and mixed-layer varieties of the above minerals and groups. The clay content of the formations can be comprised substantially of a single species of clay mineral, or of several species, including the mixed-layer types of clay. Of the clay minerals commonly encountered in the drilling of wells in natural geological formations which can be productive of 3 wise become disrupted in thepresence of aqueous fluids. A clay which swells is not limited to expanding latticetype clays but includes all those clays which can increase in bulk volume with or without dispersing, disintegrating or otherwise becoming disrupted when subjected tocontact with aqueous solutions such as water, certain brines, etc. Certain clays can also disperse, disintegrate or otherwise become disrupted without swelling in the presence of aqueous solutions such as water, certain brines, emulsions containing water or certain brines, etc. Some clays in the presence of such aqueous solutions will expand and be disrupted to the extent that they will become unconsolidated and move into .a borehole. Formations which consist largely of clay can develop pressures on the order of several thousand pounds per square inch upon'absorbing water in a confined space.

The-clay materials defined above occur as minute, plate like, tube-like and/or fiber-like particles having an extremely large surface areacompared to that of an equivalent quantity of .a granular material such as sand. This combination of small size and great surface area results in a high surface energy with attendant unusual surface properties and extreme affinity for surface-active agents. The structure of some of these clays, as for instance montmorillonite, can be pictured as a stack of sheet-like threerlayer lattice units which are weakly bonded to each other and which are expanded in the c crystallographic direction by water or other substances which can penetrate between the sheets and separate them.

A ll:clay minerals have ion-exchange properties. Thus, for example, montmo.rillonite has a cation-exchange capacity of from about 90 to- 130 milliequivalents per 100 grams :of pure clay, illite from about 20 to 40 milliequivalents, and kaolinite from about 5 to milliequivalents. Under ordinary oil-well conditions the ion-exchange reactions between the-clays and substances associated with the clays and capable of reacting therewith are essentially reversible.

The properties of the clays vary widely with the cations occupying'the base-exchange positions or sites. A baseexchange position or site can be defined as an area, in this instance on a clay crystal, which has associated with itan.exchangeablecation. Among the cations which are generally found .on the base-exchange position or site can be, mentioned sodium, potassium, calcium, magnesium,

iron, hydrogen, etc. These cations are believed-tobeheld to theclaysurface by ionic forces.

The cations occupying the base-exchange sites on :the

clay can be those originally present or cations findingtheir' way to the baserexchange position from the liquids in contact therewith. Accordingly, the nature and concentrations ofions in the water in contact with the. clay can determine the cations occupying the base-exchange sites. In mostoil well formations, the natural waters associated therewithcontain sodiumas the predominant cation, with calcium, magnesium and other cations present in much smaller quantities. Since the base-exchange positions on the. clayiare occupied by cations, in many cases the cation will :be sodium when natural ground waters such as those described above are associated therewith. Unfortunately, however, as for example in the case of the'sodium form of montmorillonite, these clay minerals swell in the .presenceiof' water or certain brines and can, in some instances, exert pressuresupto thousands of pounds per square inch, Thus, dependent upon the amount of water absorbed, the clay-can change to a rigid paste or a gelatinous mass, or

. yammoniumionscan be-spotted adjacent theiforrnationor if suflicient water is present, the clay can disperse .com-

pletely into the aqueous phase.

We have found that the difficulties noted above can be substantially reduced and a clay body can be stabilized to impart or .maintain satisfactory permeability to fluids, mproved mechanical strength and increasedresistance to :hernical attack by .treating such clay body with sub- :tituted ammoniumiions derived from heterocyclic nitroe pacity oft-the .clay.

gen compounds selected from the group consisting of h s amine lA- im hy p pe id ne, 2 2-b py.ridine. 2,2- dipyridylamine, 5-vinyl-2-methylpyridine, N-(3-aminopropyl)morpholine, and 3-(2-aminoethyl)indole. While the substituted ammonium ions defined above are effective clay-stabilizing agents, the parent basic nitrogen compounds from which the substituted ammonium ions are derived have essentially no clay-stabilizing action.

The substituted ammonium ions can be obtained, among other ways, from salts prepared by reacting an appropriate basic nitrogen compound of the class described with an acid, preferably one whose anionic component will not form a precipitatewith ions associated with substances such as aqueous fluids with which the substituted" ammonium salt may'corne in contact. Thus, if the fluids contain a significant concentration of alkaline earth ions, it is inadvisable to employ salts whose anionic component may besulfate, oxalate, etc., since a precipitate can result. Among the compounds which can be employed in preparing the salts are hydrochloric acid, hydrobromic acid, nitric acid, lactic acid, citric acid, salicylic acid, etc., lower fatty acids such as formic, acetic, propionic, etc., and methyl bromide, ethyl bromide, .isopropyl iodide, etc. Among the salts which are satisfactory for use in accordance with the present invention are histamine dihydrochloride, ZA-dimethylpiperidine hydrochloride, 2,4.-di-

methylpiperidine ,hyd-robromide, 2,4-dimethylpiperidirre acetate, 2,4vdimethylpiperidine salicylate, 2,2'-bipyridine dihydrochloride, 2,2--. ipyridylamine trihydrochloride, 5- vinyl=21methylpyridine hydrochloride, 5-vinyl-'2.-methylpyridine .propionate, -5-vinyl-'2emethylpyridine salicylate,

'3-, ('2iaminoethyl)indole citrate, and 3-(2-aminoethyl-) indole formate.

In treating the clay, substituted ammonium ions or mixtures of the substituted ammonium ions dissolved in anysuitableipolar solvent such as Water, methyl alcohol,

.ethyLalcohoL'mixed solvents, etc. can be employed. The

solution employed can be of any desired concentration,

from as little as one-hundredth molar to a saturated solu- I tion, but preferably in :a concentration of about0.75 to about one :and one-half molar.

Theramountof solution necessary to treat'the clay body andtQbt-ain ithe beneficialresults .of this invention depends on re number t-of variables, for example the .amount of clay, the: 1oncentration of the treatingsolution, the poresity of the clay body, :thedesired depth-of-penetrationinto 1 clay body and "the type of clay to be treated. Ingeneral, the Glayjs contacted with solutions of substituted ammonium :ions insuch amounts as to provide at least 1,

and preferably atleast 5, milliequivalents of substituted ammoniumiqns Per milliequivalentof base-exchange ca- In any case, best results .are obtained-bywusing an excess of substituted ammonium ions, measured as :milliequivalents, over the number .of base.

exchange positions, also measured as milliequivalents, on

the play 1 e treated.

To treatthe clay with the solutioneontaining the -subs ituted ammonium ions any suitable method that will assure effective contact between the solution and theclay can be employed. well, for-example, the. solution containing'the substituted formations, tobeztreated andthen be permitted .topen meate :the formation, pressure being used to force the solution into the formation ifsdesired. In addition, the solution :can be used to :treat an oil well :formation by spotting, prior to shooting, a sufiicient amount of the solution iin a well bore adjacent a section to be shot and then shooting. Also, in gun perforating or- :jet perforating a .well, -the solution can be spotted through the- I interval to beiperforatedand the gun .then inserted-and r In treating a formation adjacent a fired in the hole opposite the interval. In secondary recovery, such as a water flood program, the treating solution can be used in front of the flood to stabilize the clay in the formation as the flood progresses through the formation, thus precluding a drop in injection rate caused by reduced permeability due to swelling and/ or dispersing of the clay. In treating the formation adjacent a bore hole of a well which is producing hydrocarbons, the beneficial results of this invention can be obtained by treating the formation with sufficient of the treating fluid to obtain a penetration of at least one foot and preferably between about and 50 feet, and then returning the well to production.

.The mechanism involved in treating clays in accordance with our invention is an ion-exchange reaction between exchangeable cations of the clay and the substituted ammonium ions in the treating solution. When the clay is contacted with the substituted ammonium ions identified above, the substituted ammonium ions exchange quickly and in an essentially irreversible manner with the cations occupying the base-exchange sites on the clay structure. As a result of this treatment, hydrated, swollen clay will shrink essentially irreversibly, unhydrated clay will be rendered insensitive to Water and other swelling agents, and the resistance of the clay to mechanical and chemical attack will be increased.

In order to demonstrate the efiectiveness of the substituted ammonium ions identified above as clay-stabilizing agents, We have run a series of tests in which various substituted ammonium ions were employed. The substituted ammonium ions were formed by dissolving in water salts obtained by the reaction of the basic heterocyclic nitrogen compound with hydrochloric acid. Montrnorillonite was chosen as the clay for these tests because of its very high ability to swell and disperse. The tests comprised placing 0.077 gram of montmorillonite (0.077 milliequivalent base-exchange capacity) suspended in 5.0 milliliters of a salt solution in a test tube. One liter of the salt solution prior to suspending montmorillonite therein contained 2,317 milligrams of sodium bicarbonate, 279.9 milligrams of calcium chloride hydrate, 434.2 milligrams of magnesium chloride hydrate, and 0.86 milligram of magnesium sulfate. The contents of the test tube were allowed to set for 48 hours, after which the amount of precipitate was measured. The substituted ammonium ion was then added to the contents of the test tube in an amount equal to five times the base-exchange capacity of the clay and the mixture was shaken for minutes and subsequently allowed to stand for 24 hours. At the end of this period the volume of clay precipitate was estimated and such quantity of supernatant liquid was withdrawn from the test tube that the volume of the liquid and clay remaining was the same as the volume of the clay suspension originally treated. Fifteen milliliters of distilled water were added to the resulting mixture and the test tube was shaken for 15 minutes and allowed to stand for 24 hours, after which the volume of clay precipitate was again estimated. This cycle was repeated 21 number of times. At about the 15th test cycle and for one cycle only, a salt solution similar to that in which the montmorillonite was initially dispersed was substituted for the distilled water. Otherwise, the procedure was not changed. Each cycle results in a decrease in the salt concentration of the aqueous solution and the concentration of treating agent in equilibrium with the clay precipitate. .This dilution process will cause swelling and/ or dispersion of the clay if it has not been effectively stabilized. The substitution of the original salt solution for the distilled water at about the 15th test cycle is a test for the reversibility of the base-exchange reaction. Thus, if the treating agent is not held essentially irreversibly by the clay, part or all of it will be exchanged for sodium ions or other cations from the salt'solution and the claywill swell and'disperse in subsequent cycles of distilled water leaching.

The results of these tests are tabulated below in Table I Table I Compound Cycles to Cycles to Colloidal Swelling Appearand/or ance Dispersion Histamine dlhydrochloride 2,4-dimethylpiperidine hydrochlorid 2,2-bipyridine dihydrochloride 2,2-dipyridylamine trihydroehloride. 5-vinyl-2-methylpyridine hydrochloride N-1E13-aminopropyDmorpholine dihydrochlor- 3-(2-aminoethyl)indole hydrochloride Imidazole hydrochloride 10 a Benzirnidazole hydrochloride 16 a. Piperazine dihydrochloride- 6 a Piperidine hydrochloride.-. 3 18 l-ethylpiperidine hydrochloride. 17 a Morpholine hydrochloride 3 19 N-ethylmorpholine hydrochloride-.. 6 a N-phenylmorpholine hydrochloride. 17 a. N -(2-aminoethyl)morpholine dihydrochl 12 a 2-vinylpyridine hydrochloride l9 8 4-vinylpyridine hydrochloride 2 9 2-vinyl-5-ethylpyridine hydrochloride 2 a B-methyl-l-phenylpyrazclone hydrochloride... 4 19 denotes that the test was discontinued at the end of 24 cycles and no swelling, dispersion, or colloidal appearance was noted.

(a) denotes that the test had a colloidal appearance at the cycle indicated in column A but had not swelled or dispersed at the end of 24 cycles.

In the above table, by colloidal appearance it is meant that after standing 24 hours the supernatant liquid retains a turbid or opalescent appearance characteristic of that caused by the scattering of incident light by suspended colloidal particles. The appearance of such a colloidal condition indicates that the clay has not been stabilized by the substituted ammonium ion tested. By swelling it is meant that the settled volume of the clay at the end of 24 hours is at least 1 /2 times the settled volume of the clay at the beginning of the test. By dispersion it is meant that the clay is dispersed uniformly throughout the liquid so that at the end. of 24 hours no precipitate or sediment can be detected. Obviously, when the clay swells or disperses it has not been stabilized by the particular substituted ammonium ion tested.

The above table graphically illustrates the advantages of the present invention. Thus it can be seen that many substituted ammonium ions derived from heterocyclic nitrogen compounds, e. g., imidazole hydrochloride, ben-.

zimidazole hydrochloride, piperazine dihydrochloride, piperidine hydrochloride, l-ethylpiperidine hydrochloride, morpholine hydrochloride, N-ethylrnorpholine hydrochloride, N-phenylmorpholine hydrochloride, N-(Z-aminoethyl) morpholine dihydrochloride, 2-vinylpyridine hydroi i chloride, 4-vinylpyridine hydrochloride, Z-vinyl-S-ethylpyridine hydrochloride, and 3-methyl-l-phenylpyrazolone hydrochloride, are unsatisfactory as treating agents for stabilizing clays, for clays treated therewith were easily dispersed or resulted in aqueous solutions having a colloidal appearance. Substituted ammonium ions derived from heterocyclic compounds selected from the group consisting of histamine, 2-4-dimethylpiperidine, 2,2-bipyridine, 2,2-dipyridylamine, 5-vinyl-2-methyl-pyridine, N-(3- aminopropyl)morpholine and 3-(2-aminoethyl) indole, however, proved to be very effective, for even at the end of 24 cycles the clay treated therewith was unaffected by water or the salt solution.

There follow illustrative embodiments of the actual practice of the process of this invention as applied to oil wells producing from formations containing clay. It is understood that the procedures described are illustrative and the invention is not to be limited thereby.

In treating a formation adjacent the bottom of a borehole to stabilize the clay, said formation containing about 5 percent by weight of montmorillonite and having a porosity of about 15 percent, so as to attain a radial depth of treatment of at least 5 feet from the borehole, about gallons of a one-molar aqueous solution of substituted ammonium'ions derived from N-(3-aminopropyl)morpholine dihydrochloride for each foot of vertical thicknesstof. theformation to be treated isused. Whilethe: oretically only about 70 gallons of the above treating solution would be needed to react with all of the clay in theflabove, volumeof formation, an excess over the theoreticalquantity isemployed to assure rapid and complete reaction with the clay. The treating solution is introduced through a string of small diameter pipe lowered to within a few feet of the bottom of the hole andallowedto flow in by gravity. Since the treating solution has a much higher specific gravity than water, oil or ordinary oil-field brines, it will displace water or oil opposite'theformation to be treated and will then flow into the formation. As an aid in: displacing the treating solution into the formation, pressure can be employed. The treating solution is introduced into the formation slowly and allowed to remain, incontact with the formation for about 24 hours, after which the unused portion, along with produced fluid, is withdrawn from the well. It will be understood that, instead of treating formations adjacent the bottom of a borehole, any selected formation interval above the bottom of the borehole canbe treated'inaccordance with the invention by setting a bridge plug, in known manner, at the bottom-of theformation to be treated, and thereafter proceeding as described above considering the top of the bridge-plug to be the bottom of the borehole.

The process of this invention is also used to advantage in secondary recovery operations wherein a displacement' fluid such as water is applied under pressure to an oil-bearing formation by means of specially equipped inputwells penetrating saidformation-for the purpose of forcing-the oil out of the oil-bearing formation through an output-well penetrating said formation. Such operations are often-developed in what is termed a five-spot pattern, with the producing well located in the center of a square formed by water input wells at the four corners. By introducing any of the treating solutions disclosed herein into the water input wells prior to injection of water, the treating solution will move ahead of the advancing water and thus stabilize the clay in the formation-before the clay has had an opportunity to come in contact with the injection water and be deleteriously affeeted'by contact therewith; In actual practice, the treating-solution is placed adjacent the formation to be treated by-introdueing the same through a string of small diameter pipe lowered to apoint adjacent the section of the formation to be treated in the manner described in the paragraph next preceding and is followed by normal injectionof water. To establish a front of the treating solution ab'outfive-fcet thick (radially) ahead of the injection waterat a radius of about 20 feet from the borehole in a formation having the same montmorillonite content and porositydescribed above, about 650 gallons of a onemolar aqueoussolution of N-(3-aminopropyl) morpholine dihydrochloride is sufficient for each foot of thickness (vertical) of the formation to be treated. Because of prior treatment in accordance with the invention, a satisfactory-permeability of the clay during the water flood is maintained or improved, thereby leading to more efficient recovery of the fluids to be produced.

The treating solutions herein disclosed are also employed with advantage in oil-well perforating. When clay-water drilling muds aroused in rotary drilling, they seal off the openings in porous formations encountered while drilling. In well completions Where such formations are cased off-andthe casing must be perforated for production, thesealing property of clay-water muds can be-det'rirnental. Since the hydrostatic head of the mud in the borehole exceeds the formation pressure, when the casing is perforated the clay-water mud rushes into the perforated formation until a mud cake seal is established or the pressure isbalanced. This often is accompanied byafreshv water loss tothe formation, which in the clay formations described, swells. the clay which is-present. In addition, there often-results blocking of'the pe foratedi'. formation to-sueh an; extent thaton subsequent compler' j tion ofithe well the'pe'rforations have to be washed [or acidized with'reagents; known as mud; clean outi'agentsf To avoid 'such'iliflieulties inperforating operations in, accordance with; thepresent. invention, a string-pf tubing;

is lqweredinto the borehole so that its. lower end is adja:

cent-the bottom of the section .to be treated and about,

300; gallons of a suitable, oil-base. drilling fluid is intro.- duced'through the tubing to displace the elay:water;dr ill tion opposite the formation to be treated: and the-casing; The hydrostatic, head.

perforated in the usual manner. in the borehole exceeds the formation, pressureand thus. will. force the treating solution into the. formation. In this .way, the naturally-occurring .lay, whichwasexposed.

to fresh water lost to the formation fromthe clay-water. drilling-fluid, will be shrunkenjandstabilized and when.

the well is permitted to flow, or is swabbed; or pumped, the unusedv clay-stabilizing, agentin the treating. solution will be produced from the, formation. Thisoperation will. leave the, formation, substantially free from plugging byv mudcake or other hydrated. clay Thus,v by employing;

any one,v ofv the, treating agents... disclosed. herein while. perforating, the. formation. will be prevented from: being muddedoff, the harmful effects; of, fresh water onnaturally-occurring clay will be. nullified, the necessity for washingv perforations with. so-called mud acids will be eliminated, and the useofconventional clay-water drillingmuds: will be permitted in areas where. the producing;

formations contain swelling-type clays and themore ex pensiveoil-base muds arecommonly used.

Similarly'in-oilwell shooting-in open, hole1with high explosives, such asnitroglycerine, trinitrotoluene, etcathe freshly exposed formation may-alsov be;contactedpwith.a

clay-water drilling fluid with the accompanying harmful' effects described above. formation to-be treated in such case-canbe replaced with a an oil-base drillingfluid followed'by the treating solution in the mannerdescribedabove, andtheexplosive-canbe lowered into the solution and detonated in the customary manner. The beneficial'resultsobtained'in employing thetreating-solutions of the invention while-perforating-will also accompany theiruse with highexplosives:

While we have found that-the specific substituted ammonium ions disclosed herein or mixtures thereof are satisfactory'for the purposes of-this'invention, there-"are certain instances wherein it is-advantageous to employirr admixture therewith othersubstituted ammoniumions not specifically disclosed hereinbut which have similar propertiesthereto, as for example, the substituted ammonium ions disclosed in our'copending applications filed concurrently herewith, Applications Serial Nos. 469,856 to 469,861, inclusive, as well as in the other-concurrently filed copending applications in the name of William E; Brown, Applications Serial Nos. 469,854 and 469,862; For example, although by-farthe greatest-portion ofthe" base-exchange sites on a clay mineral surface will have an area approximating the average area per exchange site, a small number of sites will have an area considerably lessthanthe average. Because of the spatial configuration of their hydrophobic part, certain substituted ammonium ions will'notbe ableto occupy these" smaller sites, in whichcase it'is advantageous touse-one-or more additional substituted ammonium ions of different spatial configuration which can occupy the remaining positions andthus completethe stabilization reaction. 1 It is believed The. drilling fluid opposite" the are,

that this use is especially advantageous in the case of the mixed-layer clay minerals.

Obviously, many modifications and variations of the invention, as hereinabove set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indi cated in the appended claims.

We claim:

1. A method of stabilizing a clay-containing body which comprises contacting such clay-containing body with substituted ammonium ions derived from heterocyelic nitrogen compounds selected from the group consisting of histamine, 2,4-dimethylpiperidine, 2,2'-bipyridine, 2,2- dipyridylamine, -vinyl-2-methylpyridine N-(3-aminm propyl) morpholine, and 3-(2-aminoethyl) indole.

2. A method of stabilizing a clay-containing body as in claim 1 in which the clay-containing body comprises at least one clay mineral selected from the class consisting of the montmorillonite group, hydrous-mica group, chlorite group, and kaolin group.

3. A method of stabilizing a clay-containing body which comprises contacting such clay-containing body with substituted ammonium ions derived from N-(3-aminopropyl) morpholine.

4. A method of stabilizing a clay-containing body which comprises contacting such clay-containing body with substituted ammonium ions derived from 2,4-dimethylpiperidine.

5. A method of stabilizing a clay-containing body which comprises contacting such clay-containing body with substituted ammonium ions derived from 2,2'-bipyridine.

6. A method of stabilizing a clay-containing body which comprises contacting such clay-containing body with substituted ammonium ions derived from 3-(2-aminoethyl) indole.

7. A method of stabilizing a clay-containing body which comprises contacting such clay-containing body with substituted ammonium ions derived from S-vinyl-Z-methylpyridine.

8. A method of stabilizing a clay-containing formation adjacent a well bore which comprises contacting such clay-containing formation with substituted ammonium ions derived from heterocyclic nitrogen compounds selected from the group consisting of histamine, 2,4-dimethylpiperidine, 2,2-bipyridine, 2,2'-dipyridylamine, 5- vinyl-Z-methylpyridine, N-(3-aminopropyl) morpholine, and 3-(2-aminoethyl) indole.

9. A method of stabilizing a clay-containing formation adjacent a well bore which comprises contacting such clay-containing formation with substituted ammonium ions derived from N-(3-aminopropyl) morpholine.

10. A method of stabilizing a claycontaining formation adjacent a well bore which comprises contacting such clay-containing formation with substituted ammonium ions derived from 2,4-dimethylpiperidine.

11. A method of stabilizing a clay-containing formation adjacent a well bore which comprises contacting such clay-containing formation with substituted ammonium ions derived from 2,2-bipyridine.

12. A method of stabilizing a clay-containing formation adjacent a well bore which comprises contacting such clay-containing formation with substituted ammonium ions derived from B-(Z-aminoethyl) indole.

13. A method of stabilizing a clay-containing formation adjacent a well bore which comprises contacting such clay-containing formation with substituted ammonium ions derived from 5-vinyl-2-methylpyridine.

14. A method of recovering oil from an oil-bearing formation containing clay, wherein a displacement fluid under pressure is applied to said formation through at least one input well penetrating said formation, and wherein oil is recovered from an output well penetrating said formation, which comprises introducing a treating solution containing substituted ammonium ions derived from heterocyclic nitrogen compounds selected from the group consisting of histamine, 2,4-dimethylpiper1d1ne,

10 2,2'-bipyridine, 2,2-dipyridylamine, 5-vinyl-2-methylpyridine, N-(3-aminopropyl) morpholine, aminoethyl) indole into said input well, thereafter introducing said displacement fluid under pressure into said input well, forcing said treating solution through said formation by means of said displacement fluid, and recovering oil from said output well.

15. A method of recovering oil from an oil-bearing formation containing clay, wherein a displacement fluid under pressure is applied to said formation through at least one input well penetrating said formation, and wherein oil is recovered from an output well penetrating said formation, which comprises introducing a treating solution containing substituted ammonium ions derived from N-(3-amino-propyl) morpholine into said input well, thereafter introducing said displacement fluid under pressure into said input well, forcing said treating solution through said formation by means of said displacement fluid, and recovering oil from said output well.

16. A method of recovering oil from an oil-bearing formation containing clay, wherein a displacement fluid under pressure is applied to said formation through at least one input well penetrating said formation, and wherein oil is recovered from an output well penetrating said formation, which. comprises introducing a treating solution containing substituted ammonium ions derived from 2,4-dimethylpiperidine into said input well, thereafter introducing said displacement fluid under pressure into said input well, forcing said treating solution through said formation by means of said displacement fluid, and recovering oil from said output well.

17. A method of recovering oil from an oil-bearing formation containing clay, wherein a displacement fluid under pressure is applied to said formation through at least one input well penetrating said formation, and wherein oil is recovered from an output well penetrating said formation, which comprises introducing a treating solution containing substituted ammonium ions derived from 2,2'-bipyridine into said input well, thereafter introducing said displacement fluid under pressure into said input well, forcing said treating solution through said formation by means of said displacement fluid, and recovering oil from said output well.

18. A method of recovering oil from an oil-bearing formation containing clay, wherein a displacement fluid under pressure is applied to said formation through at least one input well penetrating said formation, and wherein oil is recovered from an output well penetrating said formation, which comprises introducing a treating solution containing substituted ammonium ions derived from 3-(2-amino-ethyl)indole into said input well, thereafter introducing. said displacement fluid under pressure into said input well, forcing said treating solution through said formation by means of said displacement fluid, and recovering oil from said output well.

19. A method of recovering oil from an oil-bearing formation containing clay, wherein a displacement fluid under pressure is applied to said formation through at least one input well penetrating said formation, and wherein oil is recovered from an output well penetrating said formation, which comprises introducinga treating solution containing substituted ammonium ions derived from S-VinyI-Z-methylpyridine into said input well, thereafter introducing said displacement fluid under pressure into said input well, forcing said treating solution through said formation by means of said displacement fluid, and recovering oil from said output well.

Lietz Nov. 11, 194i Ralston et al. May 25, 1943 (Other references on following page) 11, UNITED STATES PATENTS 12 Meadors July 15, 1952 Viles' Aug; 19;: 195-2" Lytle Nov; 1711953 Skinner June 14; .1954

FOREIGN PATENTS Germany July 9; 1-953 

1. A METHOD OF STABILIZING A CLAY-CONTAINING BODY WHICH COMPRISES CONTACTING SUCH CLAY-CONTAINING BODY WITH SUBSTITUTED AMMONIUM IONS DERIVD FROM HETEROCYCLIC NITROGEN COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF HISTAMINE, 2,4-DIMETHYLPIPERIDINE, 2,2''-BIPYRIDINE, 2,2''DIPYRIDYLAMINE, 5-VINYL-2-METHYLPYRIDINE N-(3-AMINOPROPYL) MORPHOLINE, AND 3-(2-AMINOETHYL) INDOLE. 